Relativistic short-range exchange energy functionals beyond the local-density approximation.

We develop relativistic short-range exchange energy functionals for four-component relativistic range-separated density-functional theory using a Dirac-Coulomb Hamiltonian in the no-pair approximation. We show how to improve the short-range local-density approximation exchange functional for large range-separation parameters by using the on-top exchange pair density as a new variable. We also develop a relativistic short-range generalized-gradient approximation exchange functional that further increases the accuracy for small range-separation parameters. Tests on the helium, beryllium, neon, and argon isoelectronic series up to high nuclear charges show that the latter functional gives exchange energies with a maximal relative percentage error of 3%. The development of this exchange functional represents a step forward for the application of four-component relativistic range-separated density-functional theory to chemical compounds with heavy elements.

• Publication year

  2020

• Venue

  Journal of Chemical Physics

• Publication date

  2020-02-17

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1063/5.0004926arXiv 2002.06935PMID 32505167
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Essentials of relativistic quantum chemistry.

  2020cited by this paper
• Range-separated multideterminant density-functional theory with a short-range correlation functional of the on-top pair density.

  2019cited by this paper
• Range-separated double-hybrid density-functional theory with coupled-cluster and random-phase approximations.

  2019cited by this paper
• Quantum Package 2.0: An Open-Source Determinant-Driven Suite of Programs.

  2019cited by this paper
• Four-component relativistic range-separated density-functional theory: Short-range exchange local-density approximation.

  2018cited by this paper
• Dynamical local connector approximation for electron addition and removal spectra

  2017cited by this paper
• Multiconfigurational short-range density-functional theory for open-shell systems.

  2017cited by this paper
• Standard grids for high‐precision integration of modern density functionals: SG‐2 and SG‐3

  2017cited by this paper
• Big picture of relativistic molecular quantum mechanics

  2016cited by this paper
• Blind test of density-functional-based methods on intermolecular interaction energies.

  2016cited by this paper
• Electron correlation within the relativistic no-pair approximation.

  2016cited by this paper
• Semi-segmented contraction of generally contracted basis sets by property minimization

  2016cited by this paper
• A theoretical benchmark study of the spectroscopic constants of the very heavy rare gas dimers.

  2015cited by this paper
• Concluding Remarks

  2015cited by this paper
• Advances in relativistic molecular quantum mechanics

  2014cited by this paper
• Basis convergence of range-separated density-functional theory.

  2014cited by this paper
• Going beyond "no-pair relativistic quantum chemistry".

  2013cited by this paper
• Range-separated density functional theory: A 4-component relativistic study of the rare gas dimers He2, Ne2, Ar2, Kr2, Xe2, Rn2 and Uuo2

  2012cited by this paper
• Solved and unsolved problems in relativistic quantum chemistry

  2012cited by this paper
• Recent advances and perspectives in four-component Dirac-Kohn-Sham calculations.

  2011cited by this paper
• Time-independent (static) density-functional theories for pure excited states: Extensions and unification

  2009cited by this paper
• Density functional theory

  2009cited by this paper
• Relativistic Quantum Chemistry

  2009cited by this paper
• Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science

  2009cited by this paper
• A fully relativistic method for calculation of nuclear magnetic shielding tensors with a restricted magnetically balanced basis in the framework of the matrix Dirac-Kohn-Sham equation.

  2008cited by this paper
• A direct relativistic four-component multiconfiguration self-consistent-field method for molecules.

  2008cited by this paper
• Introduction to Relativistic Quantum Chemistry

  2007cited by this paper
• A short-range gradient-corrected spin density functional in combination with long-range coupled-cluster methods: Application to alkali-metal rare-gas dimers

  2006cited by this paper
• Relativistic Quadruple-Zeta and Revised Triple-Zeta and Double-Zeta Basis Sets for the 4p, 5p, and 6p Elements

  2006cited by this paper
• Scaling relations, virial theorem, and energy densities for long-range and short-range density functionals

  2006cited by this paper
• Even tempered basis sets for four-component relativistic quantum chemistry

  2005cited by this paper
• A short-range gradient-corrected density functional in long-range coupled-cluster calculations for rare gas dimers.

  2005cited by this paper
• Short-range exchange and correlation energy density functionals: beyond the local-density approximation.

  2004cited by this paper
• Short-Range Exchange-Correlation Energy of a Uniform Electron Gas with Modified Electron-Electron Interaction

  2004cited by this paper
• Long-range/short-range separation of the electron-electron interaction in density functional theory

  2004cited by this paper
• Four-Component Electronic Structure Methods for Molecules

  2003cited by this paper
• Theoretical chemistry and physics of heavy and superheavy elements

  2003cited by this paper
• Four‐component relativistic Kohn–Sham theory

  2002cited by this paper
• Relativistic electronic structure theory

  2002cited by this paper
• Relativistic Density Functional Theory: Foundations and Basic Formalism

  2002cited by this paper
• Relativistic density functional theory using Gaussian basis sets

  2002cited by this paper
• A new implementation of four-component relativistic density functional method for heavy-atom polyatomic systems

  2001cited by this paper
• Four-component relativistic density functional calculations of heavy diatomic molecules

  2000cited by this paper
• On the eigenvalues of operators with gaps. Application to Dirac operators.

  2000cited by this paper
• A Minimax Principle for the Eigenvalues in Spectral Gaps

  1999cited by this paper
• Density-functional theory beyond the Hohenberg-Kohn theorem

  1999cited by this paper
• Why semilocal functionals work: Accuracy of the on-top pair density and importance of system averaging

  1998cited by this paper
• The Beijing four-component density functional program package (BDF) and its application to EuO, EuS, YbO and YbS

  1997cited by this paper
• Generalized Gradient Approximation Made Simple.

  1996cited by this paper
• On degeneracy, near-degeneracy and density functional theory

  1996cited by this paper
• Relativistic four‐component multiconfigurational self‐consistent‐field theory for molecules: Formalism

  1996cited by this paper
• Generalized gradient approximation for the relativistic exchange-only energy functional.

  1996cited by this paper
• Improved radial grids for quadrature in molecular density‐functional calculations

  1996cited by this paper
• Coulomb-attenuated exchange energy density functionals

  1996cited by this paper
• Local and nonlocal relativistic exchange-correlation energy functionals: Comparison to relativistic optimized-potential-model results.

  1995cited by this paper
• Density Functional Aspects of Relativistic Field Theories

  1995cited by this paper
• Kinetic balance and variational bounds failure in the solution of the Dirac equation in a finite Gaussian basis set

  1990cited by this paper
• The minimax technique in relativistic Hartree-Fock calculations

  1988cited by this paper
• Minimax principle for the Dirac equation.

  1986cited by this paper
• Hellmann-Feynman, virial, and scaling requisites for the exact universal density functionals. Shape of the correlation potential and diamagnetic susceptibility for atoms.

  1985cited by this paper
• Density Functionals for Coulomb Systems

  1983cited by this paper
• Theory of relativistic effects on atoms: Configuration-space Hamiltonian

  1981cited by this paper
• Foundations of the Relativistic Theory of Many-Electron systems

  1980cited by this paper
• Universal variational functionals of electron densities, first-order density matrices, and natural spin-orbitals and solution of the v-representability problem.

  1979cited by this paper
• A relativistic density functional formalism

  1979cited by this paper
• Inhomogeneous relativistic electron gas

  1978cited by this paper
• On the calculation of multiplet energies by the hartree-fock-slater method

  1977cited by this paper
• Inhomogeneous Electron Gas

  1973cited by this paper
• Self-Consistent Equations Including Exchange and Correlation Effects

  1965cited by this paper

• Toward a formulation of a CISS theory with the inclusion of two-particle relativistic effects, electron-phonon coupling, and electron-electron correlation. An application to NMR-based chiral discrimination.

  2025cites this paper
• Range Separation Method for Density Functional Theory Based on Two-Electron Infinite-Order Two-Component Hamiltonian.

  2024cites this paper
• DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science

  2022cites this paper
• Relativistic effects on electronic pair densities: A perspective from the radial intracule and extracule probability densities.

  2022cites this paper
• Picture-change correction in relativistic density functional theory.

  2021cites this paper
• Range‐separated multiconfigurational density functional theory methods

  2021cites this paper
• Short‐range correlation energy of the relativistic homogeneous electron gas

  2021cites this paper
• Relativistic density-functional theory based on effective quantum electrodynamics

  2021cites this paper
• Effective quantum electrodynamics 2 . 1 Free Dirac equation and quantized Dirac field

  2021cites this paper
• Mössbauer isomer shifts and effective contact densities obtained by the exact two-component (X2C) relativistic method and its local variants.

  2020cites this paper